Methyl acrylate is an important monomer for the synthesis of high molecular polymer. It can readily polymerize with other monomers to produce various polymers with different excellent properties and uses, which have been used in making a series of products, such as paints, textile aids, adhesives, dispersing agents, flocculating agents, thickening agents, water absorbents, and is extensively applied in chemical industry, textile processing, leather processing, paper manufacturing, food industry and oil extraction.
Acrylic acid was first prepared by Josoph Redten Bach in 1843 (J. Ann. 47, 125,1843) by oxidation of acrylaldehyde in the presence of silver oxide. It did not draw more attention until when 1901 Otto Rohm discovered that the polymers of acrylic acid and its ester have important industrial applications. Methods for preparing acrylic acid and its ester has been developing rapidly since then.
In 1927, Rohm and Haas in Germany invented an industrial method for synthesizing acrylic acid and its ester from cyanoethanol (Kirk Othmer, "Encyclopedia of Chemical Technology" 2nd ed., vol.1, p286). In 1953 Reppe invented a method for synthesizing acrylic acid and its ester directly from acetylene, carbon monoxide, and water or alcohol in the presence of nickel carbonyl as catalyst (Jusfus Leibigs Ann. Der chemie 582, 1, 1953). However, it was hard to solve the problem of labor protection due to the toxicity of nickel carbonyl. This process was improved by BASF Co. later. In the improved method nickel bromide was used as a catalyst, but the reaction pressure was relatively higher. On the other hand acetylene is very dangerous when being treated under a high pressure and needs special safety means. In 1958, Celanese and BF Goodrich Co. in the USA set up a unit for producing acrylic acid by using propiolactone method. In the nineteen sixties, the preparation of acrylic acid via acrylaldehyde by direct oxidization of propylene was developed successfully (Chem. Tech. June, p350-355, 1973; Kroli kowski, W. Soc. Plastic Eng. 1031, September 1964), which speeds up the development of producing acrylic acid and its ester.
Up to now, the cyanoethanol and propiolactone methods have not been used in industry due to the toxicity of cyanide and propiolactone. There are two main methods for preparing methyl acrylate, the propylene oxidation method and carbonylation method of acetylene with CO, water or alcohol. With the developing of the chemical industry, the demand of methyl acrylate is increasing. Therefore, new synthetic processes have been continuously explored to satisfy the demand of enhancing production capacity of methyl acrylate in various areas which are rich in different raw materials.